Formation of OH radicals in the gas phase ozonolysis of alkenes: the unexpected role of carbonyl oxides

Gutbrod, Roland; Schindler, R. N.; Kraka, Elfi; Cremer, Dieter

doi:10.1016/0009-2614(96)00126-1

Cited by 169 publications

(224 citation statements)

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“…A significant fraction of gas-phase CI undergoes unimolecular decomposition and these channels have been established for the simplest CI, CH 2 OO (Horie and Moortgat, 1991;Su et al, 1980;Herron and Huie, 1977). These products include OH and other free-radicals (Martinez et al, 1981;Neeb et al, 1998;Fenske et al, 2000;Gutbrod et al, 1997;Lewin et al, 2001;Aschmann et al, 2002;Ariya et al, 2000;Atkinson et al, 1995;Gutbrod et al, 1996).…”

Section: Overview Of Ozonolysismentioning

confidence: 99%

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

2007

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Abstract. The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acidozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquidphase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics.Correspondence to: G. A. Petrucci (giuseppe.petrucci@uvm.edu) Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation.

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Section: Overview Of Ozonolysismentioning

confidence: 99%

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

2007

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“…This reaction is highly exothermic (Gutbrod et al, 1996) and a fraction of the Criegee intermediates (α CI * ) is formed with an excess of vibrational energy. The energy-rich CIs can undergo further unimolecular reactions and can form OH promptly (R29) or can be vibrationally stabilized by collisional quenching with the bath gas molecules (R30).…”

Section: General Considerationsmentioning

confidence: 99%

Technical note: Measuring tropospheric OH and HO<sub>2</sub> by laser-induced fluorescence at low pressure. A comparison of calibration techniques

2008

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Abstract. The hydroxyl radical (OH) is one of the most important oxidants in the atmosphere, as it is involved in many reactions that affect regional air quality and global climate change. Because of its high reactivity, measurements of OH radical concentrations in the atmosphere are difficult, and often require careful calibrations that rely on the production of a known concentration of OH at atmospheric pressure. The Indiana University OH instrument, based on the Fluorescence Assay by Gas Expansion technique (FAGE), has been calibrated in the laboratory using two different approaches: the production of OH from the UV-photolysis of water-vapor, and the steady-state production of OH from the reaction of ozone with alkenes. The former technique relies on two different actinometric methods to measure the product of the lamp flux at 184.9-nm and the photolysis time. This quantity derived from N 2 O actinometry was found to be 1.5 times higher than that derived from O 2 actinometry. The water photolysis and ozone-alkene techniques are shown to agree within their experimental uncertainties (respectively 17% and 44%), although the sensitivities derived from the ozone-alkene technique were systematically lower by 40% than those derived from the water-vapor UV-photolysis technique using O 2 actinometry. The agreement between the two different methods improves the confidence of the water-vapor photolysis method as an accurate calibration technique for HO x instruments. Because several aspects of the mechanism of the gas phase ozonolysis of alkenes are still uncertain, this technique should be used with caution to calibrate OH instruments.

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“…The cycloaddition of ozone to TME yields a primary ozonide, which reacts further and forms a stabilised Criegee intermediate (sCI). The sCI decomposes via the hydroperoxide channel, leading to the formation of OH radicals (Gutbrod et al, 1996) with a yield of 0.92 ± 0.08 (Berndt and Böge, 2006). O 3 was produced by UV irradiation of O 2 with an O 2 flow rate of 5 L min −1 .…”

Section: Chamber Experimentsmentioning

confidence: 99%

A quantification method for heat-decomposable methylglyoxal oligomers and its application on 1,3,5-trimethylbenzene SOA

2017

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Abstract. Methylglyoxal forms oligomeric compounds in the atmospheric aqueous particle phase, which could establish a significant contribution to the formation of aqueous secondary organic aerosol (aqSOA). Thus far, no suitable method for the quantification of methylglyoxal oligomers is available despite the great effort spent for structure elucidation. In the present study a simplified method was developed to quantify heat-decomposable methylglyoxal oligomers as a sum parameter. The method is based on the thermal decomposition of oligomers into methylglyoxal monomers. Formed methylglyoxal monomers were detected using PFBHA (o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride) derivatisation and gas chromatography-mass spectrometry (GC/MS) analysis. The method development was focused on the heating time (varied between 15 and 48 h), pH during the heating process (pH = 1-7), and heating temperature (50, 100 • C). The optimised values of these method parameters are presented.The developed method was applied to quantify heatdecomposable methylglyoxal oligomers formed during the OH-radical oxidation of 1,3,5-trimethylbenzene (TMB) in the Leipzig aerosol chamber (LEipziger AerosolKammer, LEAK). Oligomer formation was investigated as a function of seed particle acidity and relative humidity. A fraction of heat-decomposable methylglyoxal oligomers of up to 8 % in the produced organic particle mass was found, highlighting the importance of those oligomers formed solely by methylglyoxal for SOA formation. Overall, the present study provides a new and suitable method for quantification of heatdecomposable methylglyoxal oligomers in the aqueous particle phase.

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Formation of OH radicals in the gas phase ozonolysis of alkenes: the unexpected role of carbonyl oxides

Cited by 169 publications

References 24 publications

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

Technical note: Measuring tropospheric OH and HO<sub>2</sub> by laser-induced fluorescence at low pressure. A comparison of calibration techniques

A quantification method for heat-decomposable methylglyoxal oligomers and its application on 1,3,5-trimethylbenzene SOA

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Formation of OH radicals in the gas phase ozonolysis of alkenes: the unexpected role of carbonyl oxides

Cited by 169 publications

References 24 publications

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

Technical note: Measuring tropospheric OH and HO&lt;sub&gt;2&lt;/sub&gt; by laser-induced fluorescence at low pressure. A comparison of calibration techniques

A quantification method for heat-decomposable methylglyoxal oligomers and its application on 1,3,5-trimethylbenzene SOA

Contact Info

Product

Resources

About

Technical note: Measuring tropospheric OH and HO<sub>2</sub> by laser-induced fluorescence at low pressure. A comparison of calibration techniques